Diallyl cyanamide copolymer compositions



Patented Apr. 24, 1951 DIALLYL CYANAMIDE COPOLYMER COMPOSITIONS Erhart K. Drechsel and John J. Padbury, Stamford, Conn., assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing.

This invention relates to the production of new materials having valuable and characteristic properties that make them especially suitable for use in industry, for example in molding, casting, coating, electrically insulating and adhesive applications, and for other purposes. More particularly the invention is concerned with polymerizable compositions comprising, by weight, (1) from 1% to 75% of diallyl cyanamide (N-diallyl cyanamide) and (2) from 25% to 99% of a compound which is different from the compound of (1), is copolymerizable therewith and which contains a CH2=C grouping or a plurality of CH2=C groupings, e. g., styrene, methyl acrylate, glycidyl methacrylate, vinyl acetate, di-

allyl phthalate, div-inyl benzene, etc., as well as with products comprising the polymerized composition. The scope of the invention also includes method features whereby new and useful synthetic compositions are produced.

Diallyl cyanam-ide is a known compound having a boiling point of about 222 C. at 760 mm.

j cyanamide imparts valuable properties, e. g., im-

proved arc-extinguishing and/or flame-resisting characteristics, to many of the copolymer compositions of the invention, while the allyl groupings permit the compound to undergo a copoly- -merization reaction with other ethylenically unsaturated monomers.

It is one of the primary objects of the present invention to prepare a new class of copolymers for use in industry.

Another object of the invention is to provide polymerizable or potentially polymerizable-molding and other compositions which have good stor- 7 age stability and which can be handled without difiiculty prior to and during fabrication. I

I trial applications,

. Application October 12,1949, Serial No. 121,066

12 Claims. (Cl; 260-855) 2- molding compositions from which can be produced clear, colored or translucent molded articles having a wide variety of domestic andindus- Another object of the invention is to prepare clear and colorless cast articles, as well aslaminated moldings havin high strength characteristics combined with other desirable properties. Another object of the invention is to improve the usefulness of diallyl cyanamide whereby its field of utilityis enhanced.

Other objects will'be apparent to those skilled in the art from the following more detailed description. r I The foregoing objectsare attained by copolymerization of diallyl cyanamide with one or more other comonomers which are copolymerizable therewith, more particularly such comonomers which contain either a single or a plurality of monomers, although under such conditions the rate of polymerization is relatively slow. Hence to accelerate the polymerization, we prefer to use a polymerization catalyst accompanied" by heat, lighter heat and light. Further detail'sjof polymerization conditions are given hereinafter.

, proportions hereinbefore mentioned, singly o'rfa plurality (two, three, four'or any desirednum- Qber) thereof, the latter often being desirable in order to improvethe compatibility and comb]- merization' characteristics of the mixture of. monomers and to obtain new and valuable copoly- 'mers having the particular properties desired 7 for a particular service application, are such Still another object of the invention is to pre-- pare synthetic materials which are particularly useful as coating compositions and as components of coating compositions. I

monomers as the unsaturated alcohol esters, more particularly the allyl, methallyl, crotyl, 1- chloroallyl, 2-chloroally1, cinnamyl, vinyl, methvinyl, l-phenylallyl, butenyl, etc., esters of saturated and unsaturated, aliphatic and aromatic, monobasic and polybasic acids such, for instance,

as acetic, propionic', butyric, valeric, caproi c,

acrylic and alpha-substitutedacrylic (including alkacrylic, e. g., methacrylic', ethacrylic, propacrylic, etc., and arylacrylic, e. g., phenyla'crylic,

etc)",- 'crotonic, oxalic, malonic, succinic, glutaric,

adipic,- pimelic, suberic, azelaic, sebacic, fumari'c,

bazole, the various allyl cyanostyrenes, the various. alpha-substituted'styrenes and "alphasub- Stitlltd ring-substituted "styrenes, eifg "alpha- 'methyl' styrene, 'alpha=mthyl para methyl" styrene, etc.;

unsaturated ethers, e. 'ig., "ethyl vinyl ether, -diallyl ether, ethylmthallyl' ether,

"etc.; unsaturated" amides, for instance N-allyl caprola'ctam, acrylam'ide, I and "N substituted acryla mides, e.' g., N-methy'lol acrylarriide, N- all'yl Iacrylamide, N-mthyl acrylafnide, N'aph'enyl acrylamide, etc. unsaturated ketones, e.. g.,

methyl vinyl ketone, 'mth'ylallyl keto'ne, etc.; methylene" malonicesters -e; g., methylene methyl malonate, etc.';' butadien'es, e. g., I,3 -butadiehe,2- chlorobutadiene, etc.; unsaturated polyhydric alcoh'ol (e. g, butenediol, jetc. esters. or: sat- ...urated and..unsaturatd,= aliphatic and. aromatic, .mon'obasic and. polyb'asic acidsjf'illustrative. ex-

P aiii'p'les of which appear above; unsaturated gly- .amethacrylate, glycidyl itaco'nate, ,gly'cidyl allyl ,bhthalate, etc.

fl q her a p ss.ib g m s'f n be copolymerized with diallyl .cyanamide to produce 3 our new. copolymer compositions; arefthe vinyl halides, more" particularly vinyl-.1 luoride,;viny1 4 chloride, vinyl bromide and vinyl iodide,/and-the various vinylidene compounds, including 'the zviny-lidene halides,=-e. g., vinylidene chloride,

.Tvifiylidene bromide, vinylidenefluoride and vinylidene iodide, other comonomers being added if "neededlin order to improve the compatability and copolymerization characteristicsoflthemixed m fi z r U Other and morespefcific examplesf, monom'eric materials 'which can benmixediorblended with' diallyl.jcyanamidein the aforementioned proportions, and the resulting homogeneousflor Substantially homogeneous; polyirielizable. composition "then polymerizeil'ashereinafter-more fully' desci'ibed', to yield new andvamobio copolymer compositions areth allyl compoufidswhioh are" differentfroml'diallyl cyanamlde and 'speorally those which have a boilingpoint of. at least about 60 0., Ofthe monomeric materials which "can'be' used the allyl esters form alarge class, all

' or which are suitable. The reactive .Tallyl. compounds employed are preferably those which have a high boiling-point such, for. example; as

{diallyl maleate, diallyl fumarate, Idiallyl.phthalatej'diallyl succin'ate, etc. -Other allylcompounds "which are not necessarily. high boiling also may can be cop'olymerizd with 'di allyl cyanamideare "one or another or aplurality of the following (or 4 a mixture thereof with another comonomemi allyl alcohol, methallyl alcohol, allyl acetate, allyl methacrylate, diallyl carbonate, allyl lactate, allyl alpha-hydroxyisobutyrate, allyl trichloro- 5 silane; allyl acr ylate, diallyl malon'ate} diallyl oxalate, diallyl gluconatej diallyl methyl'gluconate, diallyl adipate, diallyl azelate, diallyl sebacate, "diallyl tartronate, diallyl tartrate, diallyl mesa- ':-conate,"-"diallyl citraconate, the diallyl ester .10 of muconic acid, diallyl itaconate, diallyl chlorophthalate, diallyl dichlorosilane, the diallyl ester "*of endomethylene' tetrahydrophthalic anhydride, "triallyl'tricarb alllylate, triallyl aconitate, triallyl cyanur'atef triallyl citrate, triallyl phosphate, 5 trimethallyl phosphate, tertallyl silane, tetrallyl silicate henallyl disiloxane, etc. Other examples pf-allyl compounds that may be employed are givemfor example, in the copending application of Edward L. Kropa, Serial No. 700,833, filed October 2,1946, now Patent No. 2,510,503,. issued Jun 611950.

f Among the comonomers which are pre'ferrdfor use in carrying'our'invention into efiect are the 'vinyl 'compoundsgincluding' the vinyl aromatic compounds, moreparticularly the vinyl aromatic hydroc'arbons'le; g.', styrene, isopropenyl toluene, 'the various 'di'alkyl styren'es, etc.) and the vinyl aliphatic c on'ipounds,'-e." g.,. acryloriitrile, .acrylamidefetc and other compounds containing a "CHz=-C grouping, e.g., "the various'substituted acr'ylonitriles (e! g.'," mthacrylonitrile, thacrylonitrile, phenylacr'ylonitrile;Tetc.), the various sub- 's'tituted acrylamides .(e. g., methacrylamide, ethacrylamide," the various N.-substituted.- acrylamides and alkacr'ylamidesffor'instance N-methylol acryla'miclelN monoalkyl and dia1kyl acryl- (amides and methacrylamides, e. g., N-monomethyl, -ethyl, l-prop'yl, -butyl, .tc., and N-dimeth'yl, -thyl, -pr,opyl, but'yl, ..etc.,.acrylamides and methacrylamides, N-monoaryl and '-diaryl acrylamides and--alkacrylamides, e. g., N-monophenyl and -diphen'y1 acrylamides and-methacrylamides, Tetc.), vinyl-esters,- e. g., vinyl acetate, vinyl pro- 'pionate, vinyl butyrate, .vinyl isobutyrate, vinyl valerate, vinyl acrylate, vinylmethacrylate, etc., esters of. an acrylic-acid (including acrylic acid itself and the various alpha-substituted acrylic acids,- e.-: g methacrylic. :acid, ethacrylic acid, ..pheny1acrylic.acid, etc.) more particularly the alkyl-esters-ci an-acr'ylic acid, e. g., the methyl,

ethyl, propyl,. iisop'ro.p yl,.ri-butyl, isobutyl, sec.-- butyl, terts-butyl, amyl hex-yl, heptyl, octyl, decyl, adodecyl, etc.,: esters of acrylic, methacrylic, eth- --acry lic,\ phenylacr-ylic, etc., acids, including. the alkyl acrylates-:containing not-more than four wcarbon atoms inlthe a-lkyL-grouping, examples. of which are. given -above,.as-'Wel-las other vinyl aromatic and vinyl aliphatic: compounds, and: other compounds containing a-CHz=.C grouping.

mAny. suitable means .may be :used in effecting polymerization of the admixture of diallyl cyanamide and one on more other monomers which are cop'olymerizabletherewith. As has been mentioned hereinbefore heat or light or both, witn or 5 withoutell-polymerization catalyst, can be used. Ultraviolet light is more effectivethan ordinary light. Preferably: apolymerizationcatalyst is employed. -Anyof the polymerization catalysts which are suitable-for-use-in polymerizing com- 70, poundscontainingan ethylenically unsaturated -grouping, specifically a-vinyl grouping, can be employed. 1 Among-such catalysts are the inorganic peroxides, e. g.,.hydrogen-peroxide, barium c-peroxide, magnesium peroxide,-'etc.; andlthe various organic peroxy catalysts, illustrative exoxide, such peroxides often being designated as ethyl, propyl, lauryl, oleyl, stearyl, tert.-butyl and tert.-amy1 peroxides; the alkyl hydrogen peroxides, e. g., tert.-butyl hydrogen peroxide (tertbutyl hydroperoxide), tert.-amyl hydrogen peroxide (tert.-amyl hydroperoxide), etc; symmetrical diacyl peroxides, for instance peroxides which commonly are known under such names as acetyl peroxide, propionyl peroxide, lauroyl peroxide, stearoyl peroxide, malonyl'peroxide, succinyl peroxide, phthaloyl peroxide, benzoyl peroxide, etc. fatty oil acid peroxides, e. g., coconut oil acid peroxides, etc. unsymmetrical or mixed diacyl peroxides, e. g., acetyl benzoyl peroxide,

Tetralin hydroperoxide Tert.-butyl diperphthalate Cumene hydroperoxide Tert.'-butyl perbenzoate 2,4-dichlorobenzoyl peroxide Urea peroxide Caprylyl peroxide p-Chlorobenzoyl peroxide 2,2-bis(tert.-butyl peroxy) butane Hydroxyheptyl peroxide Diperoxide of benzaldehyde Other so-called free radical types of catalysts, e. g., azoisobutyronitrile (oz-,0.-biS-aZiS0bl1tyl0- nitrile) also can be used to accelerate polymerization mainly through the ethylenically unsaturated grouping. Oxygen also can be employed as a polymerization catalyst or accelerator.

I Examples of other types of catalysts that can be ufseda'recp-toluene sulfonic acid, sulfuric acid, phosphoricacid, aluminum chloride, stannic chloride, ferric chloride, boron trifluoride, boron trifiuoride-ethyl ether complex, iodine, etc. Such catalysts are especially useful when the comonomer contains a CH2=C grouping and, also, a grouping which can be ruptured and through which polymerization can occur, e. g., a dioxolane ring as in 4-alloxymethyl-2-oxo-l,3-dioxolane, 4-vinyl-l,3-dioxolane, 4-allyl-l,3-dioxolane, 4-alloxymethyl-1,3-dioxolane, etc., or an epoxy grouping as in glycidyl acrylate, glycidyl methacrylate, etc.- Such catalysts can accelerate polymerization primarily by opening up of the rupturable group- The concentration of the catalyst employed is usually small, that is, for the preferred catalysts from, by weight, about 0.5 or 1 part of catalyst per thousand parts of the polymerizable composition to be polymerized to about 3 or 4 parts of catalyst per 100 parts of the monomer or mixture of comonomers. If an inhibitor of the hind hereinafter mentioned be present, up to 6 or 7% or even more, based on the weight of the polymerizable composition, may be necessary according to the 6 organic solvents may be employed, depending upon the particular comonomer used, e. g., tolu-' ene, xylene, dioxane, ethers (e. g., dibutyl ether), esters (e. g., butyl acetate), chlorobenzene, ethylene dichloride, ketones (e. g., methyl ethyl ketone), tertiary alcohols, for instance tertiarybutyl alcohol, tertiary-amyl alcohol, tertiaryhexyl alcohol, etc., as well as others. When the reaction is effected in solution state, then a temperature at or approaching the boiling temperature of the solution generally is used.

The polymerization also can be effected by conventional bulk polymerization technique, in

the presence or absence of a solvent capable of dissolving the monomeric mixture and in which the latter preferably is inert; or in solution in a solvent in which the monomeric mixture is soluble but the copolymer is insoluble; or by conventional bead polymerization methods. The polymerization of the mixture of monomers can be effected by a continuous process as well as by a batch operation. Thus the monomeric mixture containing a trace of catalyst may be passed through a conduit with alternate hot and cool zones.

The temperature of polymerization of the polymerizab1 composition, at atmospheric or slightly above atmospheric pressure and in the presence or absence of a polymerization catalyst, can be varied over a wide range, up to and me eluding or slightly above the boiling point "(at atmospheric pressure) of the monomeric mix ture (or of the lowest boiling component thereof), but in all cases is below the decomposition temperature of the monomeric materials. In most cases the polymerization temperature will be within the range of 15 C(to 150 C.--, more particularly within the range of 20 C. or 30" C. (ordinary room temperature) to 130 C., depending upon the particular mixture of monomers employed, the particular catalyst, if any, used, the rapidity of polymerization wanted, and other influencing factors. With certain catalysts, more particularly strong acidic polymerization catalysts such, for instance, as gaseous boron trifiuoride-ethyl ether complex, concentrated sulfuric acid, anhydrous aluminum chloride, etc., a substantially lower polymerization temperature often advantageously may be used, e. g., temperatures ranging between 80 C. and 0 C. or 10 C. At the lower temperatures below the solidification point of the monomeric mixture (or components thereof), polymerization is effected while the mixture of monomers is dissolved or dispersed in a solvent or dispersion medium which is liquid at the temperature of polymerization. Or, if desired, the monomeric mixture, that is, the polymerizable composition, can be polymerized in dissolved or dispersed state at temperatures above its solidification point or above the solidification point of the polymerizable components thereof The copolymer can be separated from the liquid medium in which copolymerization was effected by any suitable means, e. g., by filtration, centrifuging, solvent extraction, etc.

In some cases it may be desirable to incorporate into the polymerizable composition an inhibitor which is adapted to inhibit copolymerization of the individual monomers present in the composition. When it is desired to use the inhibitormodified composition, a catalyst is added in an amount sufficient to promote the polymerization reaction and to yield a copolymer. Any suitable inhibitor can be used, c. g., tannin, phenol, re, sorcinol; hydroquinone, ascorbic acid, isoascorbic absent;

otherwise stated, are by weight.

Example 1 I App ox App o Parts Weight,- Mole,

r C nt- .Pe Gem:

ial v ya amid --.--.T---.-- 15 3.5 Ethx aor ta- 135 9 .6.5 Benzoylperoxide 3 are mixed together, and the resulting mixture is heatedin a closed container at 40 C. for 22 hours toyield a clear, sticky, solid,'am]oercolored resinous op y er- D ri s t ec p lym rization n exothermic reaotiontakes pla e- Thi v op lymer an .be used alone or admixed wi h variou modifiers a. a, ,r soroin leformaidehyde es ns. alkyd resins, eta, inthe pr du tion f. adheive ompositions- Example 2 Same as in Example 1 with the exception that instead of 3 parts of benzoyl peroxide there is used 3 parts of azoisobutyronitrile (alpha, a1- pha'-bis-azoisobutyronitrile) and the time of copolymerization is '20 hours instead or" 22 hours. The resulting copolymer is a clear, colorless, solid, sticky resinous mass. As in the preceding example, the reaction is exothermic. This copolymer is soluble in benzene. The benzene solution is filtered, and hexane is added to the filter solution to precipitate the copolymer. A nitrogen analysis of the dried, precipitated copolymer shows 1.48% N which corresponds to 6.e'% of diallyl oyanamide combined in the copolymer.

Example 3 Approx. Hole, Per Cent Approx. Weight, Per Cent Parts Diallyl cyanamide l. Ethyl acrylate u Benzoyl peroxide The same procedure is followed .as described under- Examples land 2 with the exception that the heating :period is 168 hours, The resulting copolymer is a clear, viscous, lemon-colored, liquid mass. When the heating is continued for an additional 552 hours, the viscosity of the liquid increases greatly and the liquid copolymer is almost clear.

Example 4 sticky, solid, resinous copo ymer; obta ne when heated o an d it ona 55 hours.

are mixed together, and the resulting mixture is heated in a closed container for 10 hours at 40 C., yielding a powdery, opaque, solidcopolymer which is'almost white in color. As in Examples 1 andz, an exothermic reactionoccurs during th v heatingperiod. Thisv copolymer is suitable. for. usein the pr duction oilfilms. filoers, rods eta, ea, by dissolvin in .a su able solvent su h as im t y o manl de, a c ncentrated aqueous solution of calcium thiocyanate, eto, a d th n sp nin the resultin solu ion o the copolymer, followed by stretching the spun fiber to orient the molecules along the fiber axis.

A copolymer having similar characteristics is obtained when 3 parts of azoisobutyronitrile is substituted for 3 parts of benzoyl peroxide in the above formulation.

Examplev ,6

ppr x. 1 App Parts Wei ht, Mole,

Per en't Per Cent Diallyl cyanamide 50 30.3 Acrylonitrile 75 50 (i9. 7 Benzoyl peroxide 3 The same procedure is followed as described under Example 5 with the exception that the time of heating at 40 C. is hours instead of 10 hours. The resulting copolymer is a tancolored, opaque, powdery, solid material.

Example 7 Same as in Example 6 with the exception that 3 parts of azoisobutyronitrile is employed in place of 3 parts of benzoyl peroxide and the heating period at 40 C. is 40 hours instead of 90 hours. The solid copp lymer which'results from the copolymerization reaction is similar to the product of Example 6 with the exception that it is lemon-colored instead of tanecolored.

Example 8 pp A r x- Parts Weight, Mole,

. Per Cent Per Cent Diallyl cyanamide i5- 10 8. 65 Styrene 90 91.35 Benzoyl peroxide 3 9 hardness (A. S. T. M. D-785,48T, Method B, Al-' pha scale) of the unfilled copolymer is 58.

Example 9 Exactly the same formulation and procedure are followed as described under Example 8 with the exception that 3 parts of azoisobutyronitrile is employed instead of 3 parts of benzoyl peroxide. The copolymer thereby obtained is a translucent, hard, solid, resinous material which is lemoncolored. Its Rockwell hardness is 53.

Example 10 Approx. Approx. Parts Weight, Mole,

Per Cent Per Cent Diallyl cyanamide 75 50 46.1, Styrene 75 50 53. 9 Benzoyl peroxide. 3

, Example 11 Same asin Example, 10 with the exception that Example 14 5 Approx. Approx. Parts Weight, Mole,

Per Cent Per Cent Diallylcyanamidefliunu'ul 1.5 1 1.05 n-Butyl acrylate....l 148.5 99 98.95 Gumene hydroperoxide -i 3. 0

A mixture of the above ingredients is heated for 480 hours at 100 C. The resulting copolymer a clear, very viscous, liquid material having a light-amber color, which can be used as a plasticizer of various synthetic resins .whichnormall have insuflicient' plastic flow. I V

The same temperature and time of heating are employed as described under Example 13. A

white, opaque, powdery, solid, thermoplastic co-' polymer of vinylidene chloride and di'allyl cya'n- 1 amide is obtained. This copolymercan be hot drawnto yield monofilaments, rods, bars, tubes, etc., having a wide variety of commercial uses.

3parts of azoi'sobutyronitrile is employed in place m e 16 of 3 parts of benzoyl peroxide. The translucent, lemon-colored liquid copolymer that is obtained Approx. App ox, after a heating period of 168 hours is a very vis- Parts filfih rer eut cous material having a considerably higher visfcosity than the liquid copolymer of Example 10 Dianylcyauamiden 30 20 after a corresponding heating period. yl ce a 1 0 80 85 Caprylylper0x1de.. 3 Example 12 I are mixed together and the resulting mixture is. Pam agg g j- ,$,{gf-- heated for 504 hours at 40? c. yielding a clean. 7

Per Cent Per Cent liquid, copolymerization product, which can be I 5 used as a plasticizer for various synthetic resins: Diallyl cyanamide. 112. 5 75 56.6 that normally have insuflicient plastic flow- Acrylonitrile 37. 5 25 43. 4 Azoisobutyronitrile 3.0 Example 17 are mixed together to form a homogeneous mass. Approx; This mixture of monomers and polymerization Parts ygg ggg bg catalyst is then heated in a closed vessel fitted with a screw top 'for 168 hours at 40 C., yielding 3 2 51 a yellow, sticky, granular, opaque, solid, resinous Cyclghgxylacrylate 147 98 97149 copolymer; which becomes gummy and rubber- 5 Benzoylpemxidemn 3 like upon standing at. room temperature for an additional 35 days. This copolymer advantageously can be used as a component of binding and adhesive compositions.

are mixed and heated together in a closed vessel 'for 24 hours at 40 C. to obtain a clear, resinous polymerization product having a light lemon color. This copolymer is especially suitable for use, e. g., in solution in an organic solvent or dispersed in water, as an agent for the treatment of 7 wool to reduce its tendency t0 shrink.

A mixture of the above ingredients is heated for 168 hours at C; A'clear, sticky, solid, resinous copolymer is obtained from the copolymerization reaction. This copolymer is suitable for use as an adhesive or as a component of adhesive compositions, as well as in the production of various coating compositions.

are mixed together and the resulting mixture is heated for 264 hoursjat 40 C. to obtain a clear,

lemon-colored; sticky. solid copolymer, which'canfi;

' Acetyl peroiidmuulnu.-.

H" be used as a modifien ot oth'r synthetic resins, aswell as in various adhesive compositions.

' .Example 19 Approx; Weight, Per Cent Approx.

Parts ole,

Per Cent Example Approx. Approx. Parts Weight; Mo Per Cent. Per Cent.

Diall yl' cyanamiiie 15' 10 8.5 S. ene l 75 50. 49.9 Ethyl acrylate 60 40 4'1. 6 Ammohutyromthla..-

The same temperature and: heating period are employed as described under Example 19. The resulting copolymer is a milky white, non-sticky, rubbery, solidmaterial.

Emmzllc. 21

Approx: Approxr Parts Weight, Mole- ,Per Cent. ,Per Cent.

Diallylcyanaziiide- 1s 10. 7.71 1 one 60 40' 36945 Ethyl-acrylate' 60. 40 37.85 Acrylonitrile A l5 10 i 17. 88 Benzoyliperoxid B These materials are mixed and heated for 168 hours at-40 .,,yieldi-ng a slightly cloud-y; lemon-- colored, solid, copolymer which is tough but not brittler It:.is: especially suitable for use in the production of laminating compositions which can be employed. in bonding together, under heat and pressure, superimposed sheets. of paper, cloth formed of cotton, nylon, glass fibers, etc, to yield are mixed together and the resulting mixture is heated to 80 C.. A slight exotherm occurs,v whereby the temperature israised to 89 C. with vigorous refluxing. An ice bath is employed to keep the temperature from going higher than 90 C. until the reaction has subsided. After a total heating periodofd hours at 85 "90' C., theresult-- ingr'brown-colored emulsion is broken by" freeztheTentirePi'eacticin masswith a; Dry 'lce acetone bath. Upon. thawing, 'theipolymer found? to be a tan-colored, elastic sticky mass. It is kneaded continuously for one hour to remove traces of ionicmatter (from the polymerization catalyst): and the emulsifying agent. The resulting product is dried in a forced-draft oven'at 70 C. for 12 hours,during which time the copolymer becomes darker in color. Analysis otthis copolymer shows 3.7% N, which corresponds to 16.15% of diallyl cyanamide combined in the copolymer.

Example 23 Approx. Approx. Parts Weight, Mole,

Per Cent Per Cent Diallyl cyanamide r- Acrylonitrile Water Sodium lauryl sulfate 1 Ammonium persulfate are mixed together, and the resulting mixture is heated to C. There is no evidence of exothermic reaction,as is the case in preparing the copolymer of Example 22. After heating for 2 hours: at -90 0., the emulsion appears to be partially broken as evidenced by the fact that some solid matter precipitates After heating for a total of 4 hours at 85'-90 C1; the reaction mixture; isa solid, granular mass. The crude copolymen is: filteredoff and washed with. water until freev ofi ionic matter and. emulsifying agent. The wet, granularcopolymeris then slurried in about 480'parts of methanol, and Wa'shed-withaniadditional: 800. parts. of. methanol to Tremor/re. any ooclude'd, unpolymerized diallyl "cyanami'de. The wet copolym'eriis then dried in a forced-draft oven for 12 hours at 70 .C- The dry copolymer is swollen but not dissolved by dimethyl formamide, indicating that some cross-linking has occurred.

In' all of the aforementioned examples, the weight and mole percentages'given' in the individual examples refer to the percentage of monomer based on the total amount of. monomers undergoing copolymerization.

Example 24 Parts 2:-amino-4,6-dialloxy-1,3,5-triazine 65.0 Diallyl tetrafluorosuccinate 30.0 Diallylcyanamide l 5.0 Benzoyl peroxide 3.0

.Eight, pliesoi. alpha-pulp paper, 10 mils thick, are coated and impregnated with. the. above mix ture of ingredients warmed to about 60 C. The impregnated sheets are super-imposed and then laminated together by heating between glass plates atv contact pressure for 2 hours at C. A. hard,.rig i.d,. laminated article is obtained.

Example 25 Parts 2,5-dichlorostyrene 72.5 Diallyl tetrafiuorosuccinate 22.5 Diallyl cyanami'de 5.0 Lauroyl peroxide 1.0

are-mixed andcopolymerized' by heating the mixture for 24 hours at 100 C), yielding a solid cop vmerhaving good flame-resisting characteristics,

13 Example 26 Parts Diallyl cyanamide 5.0 Diallyl tetrafluorosuccinate 5.0 2-amino-4,6-dialloxy-1,3,5-triazine 35.0 Ethylene glycol fumarate (crystalline) 55.0 Wood flour 66.7 Benzoyl peroxide 0.5

The above ingredients are mixed together for several. hours, compacted and sheeted. The sheets are pulverized to form a molding composition, a sample of which is molded for minutes at 100 C. under a pressure of about 50' pounds per square inch. A hard, tough, molded article having a good surface finish is obtained. Similar results are obtained when pulverized mica (325 mesh) is substituted for wood flour in the above formula.

Example 27 Parts Diallyl cyanamide Diallyl tetrafiuorosuccinate 95 Methyl methacrylate 95 Benzoyl peroxide 2 yield a hard, well-cured copolymer upon heating 7 the mixed ingredients for 16 hours at about 65 C. The hardness is further increased by heating for 2 hours at 110 C.

Example 28 Parts Styrene 91 Triallyl cyanurate .3 Diallyl, tetrafluorosuccinate 3 Diallyl cyanamide e 3 Benzoyl peroxide 1 Example 29 Parts Diallyl cyanamide 10 Glycol dimethacrylate Diallyl tetrafluorosuccinate 35 Diallyl phthalate 40 Benzoyl peroxide 1 yield a hard, substantially insoluble, substantially infusible, resinous copolymer when the mixed ingredients are heated together for 5 hours at 105- 9 Example 30 Parts Diallyl cyanamidenne 5.0 Dimethallyl tetrafluorosuccinate 7.5 Methyl 'acrylate 87.5 Benzoyl peroxide 1.0

are mixed and heated together for- 24 hours at 70 C. and for another 24 hours at 100" C., yielding a solid copolymer.

Example 31 Parts Diallyl cyanamide :10 Diallyl phthala a '35 Diethylitaconate 55 Benzoyl peroxide 1 are mixed and heated together for- 3 hours at C. yielding a hard, resinous copolymer.

Example 32 Parts Diethylene glycol fumarate sebacate 350.0 Triallyl cyanurate 37.5 Styrene 37.5 Diallyl succinate 37.5 Diallyl cyanamide .375 Benzoyl peroxide 2.5

Norm-This unsaturated alkyd resin is prepared by effecting reaction between 6 moles diethylene glycol, 5 moles fumaric acid and 1 mole sebacic acid.

' The above ingredients are mixed while warming on a steam bath to insure complete solution of the peroxide catalyst. A 2-p1y laminated article is made by curing, between glass plates, two superimposed sheets of glass cloth that are impregnated with the above polymerizable composition, for 2 hours at C. and at contact pressure. The laminate is completely cured, hard, compact, glossy, transparent and flexible. The copolymer of .diethylene glycol fumarate sebacate, triallyl cyanurate, styrene, diallyl succinate and diallyl cyanamide, which is produced in situ, fills the interstices of the sheets of glass cloth.

Example 33 This example illustrates the results obtained when an attempt is made to polymerize diallyl ,cyanamide in th absence of a copolymerizable monomer.

Parts Diallyl cyanamide Benzoyl peroxide 3 diallyl cyanamide) is obtained and there is no apparent increase in the viscosity of the supernatant liquid.

The results are almost identical when 3 parts of azoisobutyronitrile is used in placeofB parts of benzoyl peroxide in the above formulation.

It will be understood, of course, by those "skilled in the art that our invention is not limited to the particular comonomers named in the above illustrated examples, nor to the particular proportions thereof, nor to the particular methods of copolymerization given therein. Thus, instead of the specific polymerization catalysts specified in the individual examples, any other polymerization catalyst, numerous examples of which have been mentioned hereinbefore, can be employed. Depending upon the particular properties desired in the copolymer composition and the specific use intended for the composition, the comonomer can be varied as'desired or as conditions may require so long as it contains one or acsorcsc 1 more CH2=C groupings;-

different from diallyl cyanamide and is compatible and copolymerizable therewith, For instance, the copolymer' may" be a 'cyanoalkyl ester of an acrylic acid,e'. g., mono', diand tricyanomethyl esters of acrylic acid, methacrylic acid, etc., the mono- 'diand tri-(ficyanoethyl) esters of acrylic acid, methacrylic acid, etc. Or, the comonomer can beany other organic compound which is copolymerizable with diallyl cyanamide and which is-represented by the general formula whereR represents a member ofthe class consisting of hydrogen, halogen (chlorine, fluorine, brominer iodine),- alkyl (e. g., methyl, ethyl, propylbutyl to octa'd'ecyl, inclusive), includin cycloalkyl (e. g., cyclohexyl, etc), aryl (e. g., pli'enyl, xenyl, naphthyl, etc.) alkaryl' (e. g.,tolyl, x ylyl; ethylphenyl, etc.), aralkyl (e. g., benz yl, phenyleth-yl, etc.) and R representsan ar'yf radical oraradical represented by the formula ChlOI'O-l'B-b'lllifidlll, acrylonitrile, various esters of acrylic acid (e. g., methyl" acrylate, ethylacrylate, cyclohexyl' acrylate, tetrahydro'na'phthyl acrylate, decahydronaphthyl acrylate, methoXy'-- ethyl acryl'ate, ethoxyethyl acryl'ate, etc.) vv'ell as others that will be obvious to those skilled in the-art.

The polymerizable compositions of this invention comprising a mixture of diallyl cyanamide and one or more other compatible, copoiymenzable compounds containing a CH2=C grouping or a plurality of such groupings, in the weight proportions offrom 1% to 75% (e. g., or to 60- or 70%) of the former'to from to 99% (e. g., or' 40% to 80' or 90%) of the latter have a wide variety of applications. For instance, with or without a filler they can be used in the production of molding compositions and molded articles; as'the binder in the production of laminated articles; while those which are normally liquids or are'convertible' into liquids,'e. g., by dissolving in a suitable solvent, can be employed as coating compositions (or as components of such compositions) for use in finishes for wood, metals, plastics, etc., or in the treatment 'of'fibro'us materials, e. g., paper, cloth, leather, etc., oras impregnants for various porous materials such as porous metal castings, ceramic ware, fibrous materials of all kinds, etc. In using the polymerizable compositions or the liquid copolyiners in the production of laminated articles, a fibrous material, e. g., paper or sheets of cloth, asbestos, etc., is impregnated with the polymerizable composition or liquid'copolyiner. The dried, impregnated sheets are superimposed and bonded together under heat (e. g., at 40-200 C.) and pressure, for example at pressures ranging from contact pressure up to 4,000 or 5,000 or more pounds per square inch depending upon the particular composition employed. For many purposes where high strength materials are required, glass cloth is especially suitable for the production of laminates, but other fibrous materials can be employed in addition to those aforementioned, e. g., those composed of or comprising cellulose esters (e. g., cellulose acetate), regenerated cellulose fibers (e. g., viscose and cuprammonium rayons, etc), other synthetic fibers (e. g., nylon, polyacryl'onitrile fibers, fibers formed from polymeric and copolymeric vinylidene chloride compositions, etc.) as well as others. Our new polymerizable compositions and liquid copolymers also may be used in various electrically insulating applications, e. g., as coil impregnants.

The copolymers of our invention also are particularly useful in the production of molded articles. The compositions may be employed alone or admixed with a filler, dye, pigment, opacifier, lubricant, etc. Among the fillers that can be employed are alpha-cellulose pulp, asbestos fibers, cotton flock, chopped cloth cuttings, glass fibers, wood flour, mica dust, antimony oxide, titaniuini dioxide, sand, clay, diatomaceous earth, etc.

The liquid polymerizable compositions and liquid copolymers which are capable of undergoingpolymerization or further copolymerization to solid state also may be used in the production of castings. Such compositions lilnewise can be employed as adhesives, for instance, in the pro-. duction of optical devices containing a plurality of elements, examples of which are compound lenses, compound prisms, Nicol prisms, etc.

Natural or synthetic resins and other modifiers can be incorporated into the copolymeric compositions of our invention in order to modify the latter and obtain products which are especially suited for a particular application. Examples of such modifying agents are shellac, ester gum, cellulose esters and ethers, urea-aldehyde resins, aminotriazine-aldehyde resins (e. g., melamineformaldehyde resins), phenol-aldehyde resins, hydrocarbon-substituted polysil'oxane resins, e. g., methyl polysiloxane' resins, methyl phenyl polysiloxane resins, phenyl polysiloxane resins, alkyd resins, etc. Our c'opolymeric compositions alsocan be modified by incorporating therein various rubbery products such as those which comprise natural rubber, synthetic rubber-like materials,- as well as mixturesthereof.

We claim:

l. A polymerizable composition comprising, by weight, (1) from 1% to 75 of diallyl cyanamide, (2;) from 25% to 99% of a compound which is diiierent from the compound of (l), is copolymerizable therewith and which contains a CH2=C grouping, and (3) acatalyst for accelerating the copolymerization of the ingredients" of (1) and (2).

2. A product comprising a cop'olymer of copolyme'rizable ingredients including, by weight, (1) from 1% to 75% of diallyl cyanamide and 17 (2) from 25% to 99% of a compound which is different from the compound of (1), is copolymerizable therewith and which contains a CH2=C grouping.

3. A composition comprising a copolymer of copolymerizable ingredients including, by weight, (1) from to 50% of diallyl cyanamide and (2) from 50% to 95% of a vinyl compound.

4. A composition as in claim 3 wherein the vinyl compound of (2) is a vinyl aromatic compound.

5. A composition as in claim 4 wherein the vinyl aromatic compound is a vinyl aromatic hydrocarbon.

6. A composition as in claim 5 wherein the vinyl aromatic hydrocarbon is styrene.

7. A composition as in claim 3 wherein the vinyl compound is a vinyl aliphatic compound.

8. A composition as in claim 7 wherein the vinyl aliphatic compound is acrylonitrile.

9. A composition as in claim '7 wherein the vinyl aliphatic compound is an alkyl ester of an acrylic acid.

10. A composition as in claim 9 wherein the alkylester is an alkyl acrylate containing not more than 4 carbon atoms in the alkyl grouping.

11. The method of preparing a new synthetic composition which comprises polymerizing a polymerizable mixture containing, by weight,

(1) from 1% to of diallyl cyanamide and (2) from 25% to 99% of a compound which is different from the compound of (1), is copolymerizable therewith and which contains a CH2=C grouping.

12. The method of preparing a new synthetic REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Vliet Feb. 21, 1928 OTHER REFERENCES Organic Syntheses, vol. I, by Gilman et al., 2nd ed. published by John Wiley and Sons, pages 203-204.

Number 

1. A POLYMERIZABLE COMPOSITION COMPRISING, BY WEIGHT, (1) FROM 1% TO 75% OF DIALLYL CYANAMIDE, (2) FROM 25% TO 99% OF A COMPOUND WHICH IS DIFFERENT FROM THE COMPOUND OF (1), IS COPOLYMERIZABLE THEREWITH AND WHICH CONTAINS A CH2=C< GROUPING, AND (3) A CATALYST FOR ACCELERATING THE COPOLYMERIZATION OF THE INGREDIENTS OF (1) AND (2). 